Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2

Besara, Tiglet; Ramirez, Daniel C.; Sun, Jifeng; Falb, Nathaniel W.; Lan, Wangwei; Neu, Jennifer N.; Whalen, Jeffrey B.; Singh, David J.; Siegrist, Theo

doi:10.1021/acs.inorgchem.7b02265

Title: Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba₃Ln₂O₅Cl₂

Journal Article · Fri Feb 02 00:00:00 EST 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b02265· OSTI ID:1470520

^[1]; Ramirez, Daniel C. ^[2]; Sun, Jifeng ^[3]; Falb, Nathaniel W. ^[2]; Lan, Wangwei ^[4]; Neu, Jennifer N. ^[4]; Whalen, Jeffrey B. ^[2]; Singh, David J. ^[3]; Siegrist, Theo ^[5]

Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Missouri State Univ., Springfield, MO (United States). Dept. of Physics, Astronomy, and Materials Science
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Florida State Univ., Tallahassee, FL (United States). Dept. of Physics
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Florida State Univ., Tallahassee, FL (United States), FAMU-FSU College of Engineering, Dept. of Chemical and Biomedical Engineering

Single crystals of a new family of layered lanthanide oxychlorides, Ba₃Ln₂O₅Cl₂ (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba₃Ln₂O₅Cl₂ phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba₂Ln₂O₅ formed by corner-connected LnO₅ tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl₂. A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001299; FG02-09ER46577; SC0008832

OSTI ID:: 1470520

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 4; Related Information: S3TEC partners with Massachusetts Institute of Technology (lead); Boston College; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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Title: Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2

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Title: Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba₃Ln₂O₅Cl₂